Search Results (84)

Chemical complexity is not a nuisance to be minimized in origin of life research, it is an enabling condition. This second edition of the Special Issue on the Origin of Life in Chemically Complex Messy Environments gathers contributions that embrace multicomponent mixtures, dynamic geochemical settings, and nonequilibrium processes. The papers collected here survey surface hydrothermal routes to reactive nitriles, groundwater evolution of alkaline lakes, and transition metal sulfide-driven amino acid and amide formation without cyanide. They report one pot nucleoside and nucleotide synthesis from formamide over cerium phosphate, review non aqueous organophosphorus pathways, and probe peptide rich mixtures and formose type networks under serpentinization associated minerals. The issue also advances conceptual frameworks, including atmospheric photochemical signatures for biosignature discrimination, the role of chiral mineral surfaces in enantioseparation, and computational simulations of the origin of LUCA. Together, these studies position messy chemistry as a crucible that turns chemical diversity and environmental heterogeneity into routes toward organization and function. Full article

The detection of chiral properties is crucial for pharmacology and biochemistry, yet standard circular dichroism spectroscopy suffers from low sensitivity when probing minute sample volumes. While complex asymmetric chiral nanostructures can enhance these Circular Dichroic (CD) signals, their fabrication is intricate and costly. In this work, we analyzed an alternative based on extrinsic chirality in achiral square arrays of plasmonic circular NHAs realized via Displacement Talbot Lithography (DTL), thus exploring the chiroptical response arising from symmetry breaking induced by oblique illumination. Unlike isolated nanoparticles, nanohole arrays (NHAs) support propagating Surface Plasmon Polaritons (SPPs), allowing for unique light confinement capabilities essential for high-throughput sensing. A careful characterization in terms of Stokes parameters has been performed over a selected range of different optical angles of incidence and sample orientation to disentangle extrinsic chiral contribution from spurious effects related to sample imperfections. By optimizing such extrinsic chiral contributions, enhanced chiroptical response could be engineered by significantly amplifying the interaction between light and chiral biomolecules trapped within the holes. This methodology establishes DTL-fabricated achiral NHAs as an ultrasensitive, cost-effective platform for the detection and discrimination of enantiomers in biosensing applications. Full article

Integrating metasurface-based polarizing filters atop photodetectors enables the expansion of detection capabilities from intensity to polarization, offering significant potential for applications requiring high-precision discrimination in scientific, industrial, and defense sectors. However, such metasurfaces often introduce optical efficiency losses. Here, we present a long-wave infrared (8.6 μm) circularly polarized photodetector capable of direct chiral discrimination, eliminating the need for additional optical components. The polarization selectivity arises from Guided-Mode resonances (GMRs) excited by two horizontally offset right-trapezoidal unit cells within a chiral metasurface. This design exhibits a pronounced transmittance contrast (~100%) between left circularly polarized light (LCP) and right circularly polarized light (RCP) while maintaining fabrication simplicity via a conventional single-step lithographic process. The proposed detector is expected to achieve high-dimensional physical characterization by resolving polarization-encoded vectorial information, demonstrating enhanced performance in complex environments. Full article

Polarization-sensitive photodetection is critical for advanced optical systems, yet achieving simultaneous high-fidelity recognition of the circularly polarized (CP) and linearly polarized (LP) light with compact designs remains challenging. Here, we use COMSOL 5.6 software to demonstrate a silicon metasurface-integrated MCT photodetector that resolves both CP and LP signals through a single ultrathin platform. The device deciphers LP states via four orientation-specific linear gratings for differential detection, while chiral symmetric silicon nanostructures enable direct CP discrimination with an exceptional extinction ratio of 30 dB. The proposed architecture combines two breakthroughs: (1) superior polarization reconstruction capability, achieved via the synergy of grating-induced polarization selectivity and chiral near-field enhancement, and (2) a fabrication-simplified process that eliminates multilayer stacking or complex alignment steps. This work establishes a new paradigm for miniaturized, high-performance polarization optics, with potential applications in polarization imaging, quantum communication, and hyperspectral sensing. Full article

Chiral liquid chromatography (cLC) using chiral stationary phases (CSPs) has become a crucial technique for separating enantiomers. Understanding enantiomeric discrimination is essential for improving chromatographic conditions and elucidating chiral molecular recognition; the computational methods are extremely helpful for this. To assess the relevance of the association of these two approaches and to analyze the current trends, in this review, a systematic analysis of the scientific literature was performed, covering recently published works (from 2015 to January 2025) on enantioseparation by cLC using CSPs and computational studies. CSPs based on polysaccharides and Pirkle-type were the most described (accounting for 52% and 14% of the studies, respectively). Regarding the computational methods, molecular docking and molecular dynamics (MD) were the most reported (accounting for 50% and 25% of the studies, respectively). In the articles surveyed, a significant growth in research concerning both cLC enantioseparation and computational studies is evident, emphasizing the benefit of the synergy between these two approaches. Full article

A thermochromic cholesteric liquid crystal (CLC) mixture was prepared using epoxies. The structural color of the CLCN film was tuned by changing the concentration of a chiral dopant and the polymerization temperature. It was found the yellow CLCN film can be used as a sensor for the discrimination of methanol and ethanol which was proposed to be driven by the difference between the solubility parameters. Moreover, a colorful pattern was prepared based on the thermochromic property of the CLC mixture, which could be applied for decoration and as a sensor for chloroform. Full article

A novel and general approach to the practical ROMP polymerization of cinchona alkaloid derivatives providing novel hybrid materials having quinine attached on a poly(norbornene-5,6-dicarboxyimide) matrix is presented. The concept involves an easy modification of quinine (in general, any cinchona alkaloid) toward clickable 9-azide that reacts with N-propargyl-cis-5-norbornene-exo-2,3-dicarboxylic imide in Cu(I)-catalyzed Huisgen cycloaddition (click chemistry). The resulting monomers undergo a controllable ROMP reaction that leads to novel polymers of a desired length and solubility. This sequence allows for the facile preparation of a regularly decorated polymeric material having one quinine moiety per single mer of the polymer chain inaccessible using typical immobilization methods. A poly(norbornene-5,6-dicarboxyimide) type of polymeric matrix was selected due to the high reactivity of the exo-norbornene motif in Ru(II)-catalyzed ROMP and its chemical and thermal stability as well as convenient, scalable access from inexpensive cis-5-norbornene-exo-2,3-dicarboxylic anhydride (‘one-pot’ Diels–Alder reaction of dicyclopentadiene and maleic anhydride). An appropriate combination of a Grubbs catalyst, Ru(II) (G1, G2), and ROMP conditions allowed for the efficient synthesis of well-defined soluble polymers with mass parameters in the range Mn = 2.24 × 10⁴ – 2.26 × 10⁴ g/mol and Mw = 2.90 × 10⁴–3.05 × 10⁴ g/mol with good polydispersity, Đ_M = 1.32–1.35, and excellent thermal stability (up to 309°C T_d10). Spectroscopic studies (NMR and electronic circular dichroism (ECD)) of these products revealed a linear structure with the slight advantage of a trans-configuration of an olefinic double bond. The resulting short-chain polymer discriminates mandelic acid enantiomers with a preference for the (R)-stereoisomer in spectrofluorimetric assays. This concept seems to be rather general with respect to other molecules dedicated to incorporation into the poly(norbornene-5,6-dicarboxyimide) chain. Full article

Molecular alignment under strong laser pulses is an important tool for manipulating quantum states and investigating ultrafast phenomena. This review summarizes two decades of advancement in laser-driven alignment techniques, such as cross-polarized double pulses, optical centrifuges, and elliptically truncated fields. Given the prominent emphasis on transformational applications in current alignment research, we outline its importance in cutting-edge applications under strong laser pulses, such as chiral discrimination, high-harmonic generation (HHG), photoelectron angular distributions (PADs) and ionization yields in photoionization, and Terahertz (THz) manipulation. These interdisciplinary developments provide fundamental insights into ultrafast molecular dynamics. They also establish frameworks for advanced light–matter interaction control. Full article

Five chiral, racemic dialkyl α-hydroxyethylphosphonates and α-hydroxyethyl-diarylphosphine oxides were prepared in a scalable manner. Possibilities for the optical resolution of the racemic hydroxyphosphine oxides were explored via diastereomeric complex-forming experiments. The acidic calcium salt of O,O′-dibenzoyl-(2R,3R)-tartaric acid and O,O′-di-p-tolyl-(2R,3R)-tartaric acid were chosen as the resolving agents. The role of the solvent in the enantiomeric discrimination was investigated. The diastereomeric complex could be obtained in a crystalline form for α-hydroxyethyl-diphenylphosphine oxide and α-hydroxyethyl-bis(4-methylphenyl)phosphine oxide. However, in the third case, for α-hydroxyethyl-bis(3,5-dimethylphenyl)phosphine oxide, there was no chiral discrimination. Decomposition of the recrystallized diastereomeric complex followed by decomposition of the complex yielded the target compounds in 77/90% enantiomeric excess. The absolute configuration of the hydroxyethyl-diphenylphosphine oxide was determined by single-crystal X-ray diffraction measurements. The interactions stabilizing the supramolecular associate were evaluated. Full article

An asymmetric synthesis is a favorable approach for obtaining enantiomerically pure substances, but racemic resolution remains an efficient strategy. This study aims to elucidate the chiral resolution of aromatic amino acids and their elution order using glycopeptides as chiral selectors through molecular docking analysis. Chiral separation experiments were conducted using Vancomycin as a chiral additive in the mobile phase (CMPA) at various concentrations, coupled with an achiral amino column as the stationary phase. The Autodock Vina 1.1.2 software was employed to perform molecular docking simulations between each enantiomer (ligand) and Vancomycin (receptor) to evaluate binding affinities, demonstrate enantiomeric resolution feasibility, and elucidate chiral recognition mechanisms. Utilizing Vancomycin as CMPA at a concentration of 1.5 mM enabled the separation of tryptophan enantiomers with a resolution of 3.98 and tyrosine enantiomers with a resolution of 2.97. However, a poor chiral resolution was observed for phenylalanine and phenylglycine. Molecular docking analysis was employed to elucidate the lack of separation and elution order for tryptophan and tyrosine enantiomers. By calculating the binding energy, docking results were found to be in good agreement with experimental findings, providing insights into the underlying mechanisms governing chiral recognition in this system and the interaction sites. This comprehensive approach clarifies the complex relationship between chiral discrimination and molecular architecture, offering valuable information for creating and improving chiral separation protocols. Full article

This study proposes a two-step process to design a chiral sensor combining MIP (molecularly imprinted polymer) and electrospinning technologies. First, stereoselective S(-)-limonene molecularly imprinted polymer nanoparticles (MINPs) were fabricated and dispersed into polyvinylpyrrolidone–carbon nanotube (PVP-MWCNT) conductive nanofibers to cover resistive interdigitated electrodes (IDEs). The electrical and sensing performances of the resulting sensor confirmed its capacity to discriminate and quantify the two limonene enantiomers. The sensor’s response to terpene gases appeared completely reversible, probably due to the peculiarity of the nanostructure. The sensor characteristics were influenced by the polymer matrix’s composition ratio, the cavity shape and the interfaces with carbon nanotubes. The morphological properties of the nanofibers were investigated by microscopy (optical, SEM, TEM and AFM). Full article

We present an integrated device combining a double L-shaped chiral metasurface with long-wavelength GaAs/AlGaAs quantum well infrared photodetectors (QWIPs), achieving a circular polarized extinction ratio (CPER) as high as 45 in the long-wavelength infrared range of 7–9 μm. The unit of the chiral metasurface array consists of two structurally identical L-shaped gold structures with central symmetry. The CPER of the double L-shaped QWIPs is 14 times higher than that of a single L-shaped QWIP. The device operates in three modes within the detection band: the microcavity mode, the surface plasmon polariton (SPP) mode, and the hybrid mode. The double L-shaped chiral structure selects and reflects a small portion of left-handed circularly polarized light (LCP), while the majority enters the device and excites SPP modes with the bottom gold grating layer, leading to an absorption enhancement. In contrast, right-handed circularly polarized light (RCP) is mostly reflected with limited excitation of SPP waves. QWIPs exhibit a peak absorption of 0.8 and a coupling efficiency of 2700% in the active region of the quantum well due to the combined effects of the microcavity and SPP modes, in which the SPP mode plays a dominant role. The proposed device maintains high circular polarization discrimination capability under large incident angles and can be applied in spectral imaging. Full article

Humans always identify persons through their characteristics, salient attributes, and these attributes’ locations on the body. Most person re-identification methods focus on global and local features corresponding to the former two discriminations, cropping person images into horizontal strips to obtain coarse locations of body parts. However, discriminative clues corresponding to location differences cannot be discovered, so persons with similar appearances are often confused because of their alike components. To address the above problem, we introduce pixel-wise relative positions for the invariance of their orientations in viewpoint changes. To cope with the scale change of relative position, we combine relative positions with self-attention modules that perform on multi-level features. Moreover, in the data augmentation stage, mirrored images are given new labels due to the conversion of the relative position along a horizontal orientation and change in visual chirality. Extensive experiments on four challenging benchmarks demonstrate that the proposed approach shows its superiority and effectiveness in discovering discriminating features. Full article

This paper describes the development of a simple voltammetric biosensor for the stereoselective discrimination of myo-inositol (myo-Ins) and D-chiro-inositol (D-chiro-Ins) by means of bovine serum albumin (BSA) adsorption onto a multi-walled carbon nanotube (MWCNT) graphite screen-printed electrode (MWCNT-GSPE), previously functionalized by the electropolymerization of methylene blue (MB). After a morphological characterization, the enantioselective biosensor platform was electrochemically characterized after each modification step by differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS). The results show that the binding affinity between myo-Ins and BSA was higher than that between D-chiro-Ins and BSA, confirming the different interactions exhibited by the novel BSA/MB/MWCNT/GSPE platform towards the two diastereoisomers. The biosensor showed a linear response towards both stereoisomers in the range of 2–100 μM, with LODs of 0.5 and 1 μM for myo-Ins and D-chiro-Ins, respectively. Moreover, a stereoselectivity coefficient α of 1.6 was found, with association constants of 0.90 and 0.79, for the two stereoisomers, respectively. Lastly, the proposed biosensor allowed for the determination of the stereoisomeric composition of myo-/D-chiro-Ins mixtures in commercial pharmaceutical preparations, and thus, it is expected to be successfully applied in the chiral analysis of pharmaceuticals and illicit drugs of forensic interest. Full article

Of the wide variety of toxic compounds produced by cyanobacteria, the neurotoxic amino acid β-N-methylamino-l-alanine (BMAA) has attracted attention as a result of its association with chronic human neurodegenerative diseases such as ALS and Alzheimer’s. Consequently, specific detection methods are required to assess the presence of BMAA and its isomers in environmental and clinical materials, including cyanobacteria and mollusks. Although the separation of isomers such as β-amino-N-methylalanine (BAMA), N-(2-aminoethyl)glycine (AEG) and 2,4-diaminobutyric acid (DAB) from BMAA has been demonstrated during routine analysis, a further compounding factor is the potential presence of enantiomers for some of these isomers. Current analytical methods for BMAA mostly do not discriminate between enantiomers, and the chiral configuration of BMAA in cyanobacteria is still largely unexplored. To understand the potential for the occurrence of D-BMAA in cyanobacteria, a chiral UPLC-MS/MS method was developed to separate BMAA enantiomers and isomers and to determine the enantiomeric configuration of endogenous free BMAA in a marine Lyngbya mat and two mussel reference materials. After extraction, purification and derivatization with N-(4-nitrophenoxycarbonyl)-l-phenylalanine 2-methoxyethyl ester ((S)-NIFE), both L- and D-BMAA were identified as free amino acids in cyanobacterial materials, whereas only L-BMAA was identified in mussel tissues. The finding of D-BMAA in biological environmental materials raises questions concerning the source and role of BMAA enantiomers in neurological disease. Full article